ES2266699T3 - URETANO DE UREA POLIMERICO AS AGENT OF REOLOGICAL CONTROL AND PROCEDURE FOR THEIR DEVELOPMENT. - Google Patents

Abstract

Polyurea-urethane (I) is obtained by (1) reacting a stoichiometric excess of diisocyanate(s) (II) with polyol(s) (III) to give a mixture (IV) of urethane prepolymer, NCO-terminated on both sides, and excess (II); and (2) reacting (IV) with a mixture of primary monoamine(s) (V) and primary diamine(s) (VI), with 0.1-45 equivalents (VI)/100 equivalents (V) + (VI), to (I) free from (II), (V) and (VI). Reaction is carried out in a polar aprotic solvent. An Independent claim is also included for preparation of (I) in this way.

Description

Polymeric urea urethane as an agent of rheological control and procedure for its elaboration.

The invention relates to urea urethane polymeric in polar aprotic solvents for use as rheological control agent of liquid polymers or solutions of these polymers, which can be used as agents of layer coating, casting and molding masses or substances adhesives, in the broadest sense. The invention relates also with the procedure for the elaboration of this urethane of polymeric urea

To influence the rheology of the systems liquid polymers, predominantly bentonite Organic modified, silicic acids, hydrogenated castor oil and polyamide wax. A drawback of these substances is that, they usually represent dry solid substances, which should be disintegrate / treat by solvents and shear forces to give a semiproduct, and / or are introduced by selective control of temperature in the liquid polymer system. If these temperatures they are not maintained, they appear in the final coating system crystallites, which can lead to coating failures.

The general inconvenience of these materials rheological auxiliaries used today is that they lead to cloudiness and veil formation (Haze) in clear coatings, transparent. In addition, treatment with dry products, in powder, which originate powder in processing, is not desired by technical reasons for production and hygiene at work.

Other recommendations for rheological control are described in EP-A-0 198 519, US-A-4 311 622 and the US-A-4 677 028, where it is done react polyisocyanate or polyisocyanurate with mono- or polyamines in the mandatory presence of a binder to give polyureas. This polyurea is obtained in the form of finely microdispersed crystals and thus forms a binder that prevents dripping, which is offered then as "Sag Control Agent" (SCA).

EP-A-0 435 428 describes binder systems, which have properties of rheological control, in which polyisocyanate is reacted with polyamines and monoamines in the presence of a polymer forming film containing carboxylic groups. Carboxylic groups can be reacted later with alkali to give the corresponding salts. US-A-4 882 408 also describes viscosity polyurethane systems controlled, which are made by mono- and / or reaction polyamines with mono- and / or polyisocyanates in the presence of 1 polyurethane binder component. In the US-A-4 383 068 and the US-A-3 893 956 are described procedures, in which adducts are reacted from monoalcohol polyisocyanate with dissociates and, if necessary, dissociates with primary and, if necessary, secondary polyamines in the mandatory presence of binders to give urea adducts and showing this binder then a control property rheological On US-A-4 261 845 you describe polyureas for thickening oils. It's about here of the reaction of alkoxylated monoamines with dissociates for get the corresponding diurea. The oils are thickened like this to Give high viscosity greases. The EP-A-1 152 019 describes adhesives and monocomponent thixotropic sealants, which are made by making react the isocyanates preferably with butylamine in a reactive carrier material (a polyol being preferred), to give urea.

In all these modes of execution are developed the di- or polyureas in a binder or carrier medium. The agents rheological control cannot be made alone, without these carrier means and therefore have only limited use.

US-A-4 522 986 describes urea urethane compounds, which are made by reaction of a NCO double termination urethane prepolymer, with an ethanolamine, to obtain rheological control agents with hydroxyuretic termination These urethane prepolymers of NCO termination are obtained by reacting a polyol of polyether with a stoichiometric excess of a polyisocyanate cyclic aliphatic. Urea urethane compounds are isolated, either by evaporation as waxy substances or by dilution with, for example, acetone, the compounds are isolated insoluble diurea as crystalline substances, filtered and discarded and urea urethanes that remain in solution are isolates by distillation of the diluent as waxy substances solid. A drawback of this procedure is that although it reacts the stoichiometric excess of disocyanate with the alkanolamine, however, must then be removed and discarded, since that these ureas are insoluble in polymer solutions could lead to defects.

On US-A-6 316 540 polyurethane thickeners for aqueous systems are described, which consist of a product of the polymerization reaction of a polyether polyol and a di- or triisocyanate, which are reacted  with a closing component of the linear terminal group, di-functional and polar, that is to say about 1 Isocyanate equivalent is used approximately double equivalents of the group's difunctional closure component terminal. On this occasion, polyurethane thickeners are obtained hydrophilic with functional terminal group with molecular weights of approximately 10,000-30,000 g / mol. A inconvenient in this procedure is the difficult reaction of control in the transformation of di- and triisocyanates with polyols. Known masses produce slight reactions of chain, which can only be avoided by very strong dilution in the appropriate solvents. These solvents are due then distill again and replace with appropriate solvents, like butyl glycol and water.

In the American patent US-A-4 314 924 describes a procedure for the preparation of a thixotropizer, which avoids any of the aforementioned drawbacks, in which they are described urea urethanes, which are made in aprotic solvents, in presence of lithium salts, by reaction of adducts of isocyanate with polyamines. The products thus elaborated present, however, significant inconveniences, conditioned because through the elaboration procedure, there is no monoadduct pure available, but mixtures of monoadducts are produced and dissociates, which then lead to growth with diamines uncontrolled urea urethane chain. These products they tend after the appearance of precipitates and only remain in dissolution with great difficulties.

On US-A-6 420 466 describes a procedure for the development of a thixotropizer, which avoids the inconveniences described above and leads to selective urea urethanes, which form, together with salts lithium, clear solutions and resistant to storage in polar and aprotic solvents. The inconvenience of these products is based on that, due to selective urea diurethanes prepared now only few urea groups can be introduced active in the molecule and with it a limited effectiveness is given to these urea urethanes. In addition, the subsequent elimination of excess Stoichiometric disocyanate by vacuum distillation is a Luxurious and expensive procedure. The purpose of the present invention was to find easy-to-elaborate rheological control agents, which in not presenting the aforementioned problems the patents before mentioned.

Surprisingly it is evident, that in the reaction of isocyanate terminating urethane prepolymers with mixtures of monoamines and polyamines, in certain relationships with each other, notable control agents can be developed rheological The rheological control agents according to the invention they are polymeric urea urethanes, obtainable by a first reaction of a disocyanate with a polyol, where the disocyanate is use in excess, so that a urethane prepolymer of double NCO termination, in addition to excess disocyanate, and followed of a second reaction of the double prepolymer mixture of NCO double terminated urethane and excess disocyanate, by one part, with a mixture of a primary monoamine and a diamine primary, on the other hand; in which based on 100 equivalents of the mixture of primary monoamine and primary diamine are used in 0.1 to 45 equivalents of the diamine, with the proviso that after second reaction polymer urea urethane is found considerably free of isocyanate and monoamine and diamine used, and can also be used as disocyanate, polyol, monoamine and diamine mixtures of disocyanates, polyols, monoamines or diamines Particular ways are set forth in claims 2 to 11. of execution. Urea urethane polymers conforming to the invention are preferably made in polar solvents aprotic such as, for example, N-methylpyrrolidone, N-Butylpyrrolidone, N-cyclohexyl pyrrolidone, dimethylsulfoxide, dimethylformamide or dimethylacetamide, if necessary, in the presence of soluble lithium compounds, such as lithium chloride or lithium nitrate Substantially viscous solutions are obtained clear, even slightly cloudy, with a body content 10-70% solids, preferably from 25-50%; or rigid waxy solutions, which can be transformed back into an applicable liquid form by means of a slight heating at approximately 40-70 ° C.

In addition to polymeric urea urethanes themselves themselves, the invention relates to the process for preparation of polymeric urea urethanes conforming to the invention. According to the procedure according to the invention it is done react in a first reaction of a disocyanate with a polyol, where disocyanate is used in excess, so that a NCO double termination urethane prepolymer, in addition to excess disocyanate, and followed by a second reaction of the mixture of double NCO double termination urethane prepolymer and excess disocyanate, on the one hand, with a mixture of a primary monoamine and a primary diamine, on the other hand; in the which based on 100 equivalents of the primary monoamine mixture and Primary diamine is used from 0.1 to 45 equivalents of the diamine, with the proviso that after the second reaction urea urethane polymeric is considerably free of isocyanate and of the monoamine and diamine used, and can also be used as disocyanate, polyol, monoamine and diamine mixtures of disocyanates, polyols, monoamines or diamines. In claims 13 to 15 there are particular ways of executing the procedure.

For the preparation of prepolymers of urethane polyols are reacted, such as polyalkylene polyols, polyalkenyl polyols, polyether polyols or polyester polyols or polyols mixed with polyesters and polyethers  with preferably 2 hydroxy terminal groups, from now called diols, with a stoichiometric excess of dissociation to give urethane prepolymers of NCO termination. The elaboration of the termination urethane prepolymers NCO is state of the art and is carried out according to the current procedure in the polyurethane industry. Termination Prepolymers Isocyanate is marketed by BAYER AG, for example, under the designation Desmodur E 22 as well as Huntsman Polyurethanes, for example, under the name Suprasec 1412.

The functionality of urethane prepolymers NCO termination is ≥2, preferably between 2 and 3. The functionalities> 2 are performed so that, depending on the reaction conditions, termination urethane prepolymers NCOs may also contain allophanate groups, which are formed by  reaction of urethane groups produced with NCO units free available and thus causing greater functionality. These allophanate groups are divided, in the next reaction between diol / disocyanate adducts and the mixture of amines, again in urethane and free isocyanate, which reacts with additional amine to give urea. Stoichiometric excess of disocyanate should be calculated from so that for each equivalent of diol available, more than 2 equivalents of isocyanate in the reaction, preferably between 3 and 10 equivalents, especially between 5 and 7 equivalents. How the expert already knows, they are formed in this reaction, depending on the stoichiometric excess of free disocyanate, in addition to the adduct of 1 mole of diol and 2 moles of disocyanate also homologs of higher chain and high molecular weight.

The non-transformed fraction of disocyanate after the reaction with diol is not eliminated, contrary to what was learned in US-A-6 420 466, but it is introduced into the reaction with the mono- / diamine mixture in The process of polyurea formation.

The formation of the polyurea from the diol / disocyanate adduct mixture and mono- / diamine mixture proceeds so that, after the complete reaction, no free isocyanate is available, that is, for 1 equivalent of diol / disocyanate adduct 1 equivalent of the mixture of amines is used, where between 0.1 and 45 equivalents are applied, preferably between 1 and 35 equivalents and most especially between 3 and 25 equivalents of diamine, based on 100 equivalents of the mixture of amines. It is important that all free isocyanate groups are reacted and that after the reaction the presence of any NCO groups is not verified. The amines should also be quantified so that there is no considerable excess of free amine after the reaction in the reactor. Few concentrations of triol components can be tolerated in this process, since they can behave as impurities in polyols. It is beneficial to eventually extract the water available in the polyols before the reaction with the disocyanate. The preparation of polymeric urea urethanes according to the invention can be verified in a heated and cooled closed agitator, where polar solvents, aprotic with mono- and diamines and, if necessary, lithium compounds have preferably been previously deposited. Lithium salts can be added to the urea solution also after the reaction. As soon as the lithium salts dissolve, the urethane prepolymer is applied with stirring in an amine solution. The reaction is exothermic and can easily be kept under control by cooling. The reaction can be carried out at room temperature or high temperatures up to the boiling temperature of the diluent used, preferably at temperatures between 40
and 80 ° C.

For the elaboration of urea urethanes polymers according to the invention polyethers or polyester diols, such as polyalkylene oxides, such as polyethylene glycols, polypropylene glycols, polybutylene glycols, polytetrahydrofuranodiols, as well as oxide polymers of mixed alkylene, such as polyoxyethylene polyoxypropylene glycols, where alkylene oxides can be found statistically  or in block form. Diols are especially appropriate of polyether mixed with propylene oxide, since they tend less to crystallize Polyether diols can also be made, while the oxalkylation of linear or cyclic diols ends, such as 1,4-butanediol, 1,6-hexanediol, 1,10-decanediol, 1,2-pentanediol, 2,2-dimethyl-1,3-propanediol, 2,5-dimethyl-2,5-hexanediol, 2-buten-1,4-diol, 2-butin-1,4-diol, cyclohexanedimethanol and bisphenol A. For tolerance control of polymeric urea urethane in polymers is beneficial, copolymerize small concentrations of styrene oxide in the polyether, this can be done statistically or in block. In addition to polyether diols, they can also be used polyester diols, which are preferably made by polymerization with ring opening of lactones, such as example, ε-caprolactone and / or δ-valerolactone, but also by self-condensation of hydroxycarboxylic acid, such as hydroxystearic acid or by acid condensation dicarboxylic and diols. As a final component for the formation of polyesters with ring opening can be used diols appropriate for alkoxylation, such as 1,4-butanediol, 1,6-hexanediol, etc. However, it is also possible to use mixed diols of polyether / polyester, which, for example, are made using polyoxyalkylene glycol lactones as initial components for ring opening polymerization, as described previously. It is equally possible, proceed in reverse and subsequently alkoxylate polyester diols. Here you can use known alkylene oxides, such as ethylene oxide, propylene oxide, butylene oxide and styrene oxide. In addition to the above-mentioned diols can also be applied polycarbonate diols, marketed by UBE Industries, Ltd. under the designations UH-CARB50, UH-CARB100, UH-CARB200, UH-CARB300 and / or as UC-CARB100 (the numbers represent again the tenth of the molecular weight approximate), based on 1,6-hexanediol or 1,4-cyclohexanedimethanol. They are also polyols appropriation, in the sense of the invention, for example, polybutadiene diols or their hydrogenated derivatives, marketed by Nippon Soda Co., Ltd. under the name Nisso Gl-1000, 2000 and 3000 (the numbers represent the approximate molecular weight of hydrogenated polybutadiene diols). I also know apply dihydroxy functional copolymers of ethylene and butylene, marketed as Kraton Liquid L-2203 by Kraton polymers. Other diols are, on the other hand, for example, dihydroxy functional polydialkylsiloxanes such as, for example, α, β-bis (3-hydroxypropyl) -polydimethylsiloxane.

The molecular weight of the diols used are is between 100 and 4,000 g / mol, preferably between 190 and 2,000 g / mol and especially between 500 and 1,500 g / mol.

For the reaction of these diols described above with diisocyanates, diisocyanates are appropriate aliphatic, cycloaliphatic and aromatic alone or in mixture. These isocyanates generally have the Formula

OCN-R-NCO

where R can be arylene, alkylarylene and alkylene. Special examples of these dissociations they are: 1,4-tetramethylenedisocyanate, 1,6-hexamethylene isocyanate, 2,2 (4), 4-rimethyl-1,6-hexamethylene isocyanate,  1,10-decamethylene isocyanate, 1,4, -cyclohexylenedisocyanate, p-phenylene disocyanate, m-phenylene disocyanate, 2,6-oluenedisocyanate, 2,4-toluenedisocyanate and mixtures thereof, p- and m-xylylenedisocyanate, and 4-4 ', - disocyanodicyclohexylmethane. Are used preferably 4,4'-disocyanodiphenylmethane, 3,3'-dimethyl-4,4'-bisphenylenedisocyanate, 3,3'-dimethyl-disocyanodiphenylmethane and, especially, mixtures of isomers 2,4'-y 4-4'-disocyanodiphenylmethane, which they are marketed, for example, as a mixture of isomers in a ratio 55 +/- 5% of the 2,4- and> 38,5% isomer of the 4,4- isomer as Desmodur 2460 M from BAYER AG and as a mixture of isomers in a 30% ratio of 2,4- and 70% isomer 4,4- as suprasec x 1004 from the manufacturer Huntsman. The advantage of this mixture of isomers it is based on the fact that these products are liquid and, consequently, can manipulate easily.

A large number of polyols and dissociates previously described, as well as the termination adducts isocyanate, are described in Kurt C. Frisch, Fundamental Chemistry and Catalysis of Polyurethanes, pages 3-10 and 12-18. In the subsequent reaction of the diols of NCO termination to obtain polymeric urea urethanes according to the invention are employed, as described previously, mixtures of primary monoamines and primary diamines.  In the case of monoamines, these are aliphatic amines, Araliphatic and aromatic. In the case of aliphatic amines, employ linear, branched or cyclic amines of length of string C 2 -C 8 {, for example, ethylamine, propylamine, isopropylamine, butylamine, sec- and tert-butylamine, 3-methyl-1-butamine,  hexylamine, 2-ethylhexylamine, octylamine, cyclopentylamine and cyclohexylamine. In the case of amines Araliphatic is about products, such as benzylamine, 1- and 2-phenylethylamine, 4-methoxyphenylethylamine, β- (3,4-dimethoxyphenyl) ethylamine, 1-methyl-3-phenylpropylamine and furfurylamine. Phenylethylamine is preferred and especially benzylamine In the case of aromatic amines it is considerably of phenylamine, o-toluidine, 2,6-xylidine and benzene acid hydrazine. Hydroxy functional monoamines are discarded.

In the case of diamines it is about aliphatic, araliphatic and aromatic primary diamines, such as for example, hydrazine and its derivatives, such as dihydrazine of oxalic acid, succinic acid dihydrazine, dihydrazine adipic acid and dihydrazine of terephthalic acid, ethylenediamine, neopentanediamine, 1,2- and 1,3-propanediamine, 1,6-hexamethylene diamine, 1,8-octamethylenediamine, 1,12-dodecamethylenediamine, cyclohexyldiamine, 4,4'-diaminodicyclohexylmethane, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, isophorondiamine, 4,7-dioxadecane-1,10-diamine, 4,7,10-trioxadecane-1,13-diamine, polyoxyalkylene diamines with an average molecular weight between 148 and 400 g / mol, p- and m-xylylenediamine, 4,4'-diaminodiphenylmethane and 3,3'-dimethyl-4,4'-diaminodiphenylmethane. M-xylylenediamine is preferred and, very especially, p-xylylenediamine. Monoamines They can be used as a mixture, as well as diamines.

On the other hand, it can be used in addition to the monoamine / diamine mixture also proportionally water, since it forms the corresponding diamine as intermediary of the dissociation, which reacts with other isocyanate groups still available to give polyureas

As lithium salts, LiCl or LiNO_ {3}, however, LiNO_ {3} is preferred. The content in solids of urea urethane solutions thus produced amounts to 5-80%, preferably 20-60%, especially preferably at 25-50% The reaction of NCO prepolymers with the monoamine / diamine mixture is carried out in a polar solvent aprotic, such as: dimethyl sulfa, N, N-dimethylformamid, N, N-dimethylacetamide, N-methylpyrrolidone, N-butylpyrrolidone or comparable alkyl pyrrolidones. The proportion of lithium compounds amounts to 0.2-2 moles, preferably at 0.5-1.5 moles, especially preferring 0.6-1 moles, based on the amino equivalent of the monoamine / diamine mixture used.

Urea urethanes thus produced do not contain neither free isocyanate groups nor free amino groups. They are correspondingly physically harmless. Besides, I don't know produce negative side reactions with binders or filling materials The storage stability of these urea urethane solutions so elaborated is high and amounts to Normal storage temperature up to 6 months or more.

Polymeric urea urethanes according to the invention are employed as rheological control agents in systems liquid polymers Between applications as a control agent rheological conforming to the invention are particularly found named in claims 17 and 18. These systems Polymers may contain solvents, which can be however also reagents and are formed, at the same time, in the polymer system during the hardening process of the solutions polymeric

For liquid polymer systems should understood as prepared, which in a non-hardened state are liquids or pasty and can be transported after application or other processing, usually by thermal process although also by other mechanisms, such as, for example, radical solid state copolymerization or polyaddition. These they are, for example, varnishes, nail polishes, materials floor covering, molding masses, rolling resins, adhesives, sealants, flashing and plaster, PVC and plastic plastisols printing inks All these systems have the property of drain on vertical surfaces, penetrate deeply into, for example, textile carriers or not allowing any position punctual punched during gluing. Filling materials and pigments, such as CaCO 3, Al (OH) 3, Mg (OH) 2, quartz flour, Fe 2 O 3, CrO2, TiO2, mica, etc., sediment strongly in these liquid systems and can be stirred again only hard. Light filling materials, such as spheres of hollow glass, rise and separate from the system. In all these systems it is necessary to apply rheological agents, to eliminate these inconveniences. They are varnishes and / or coating agents in the meaning of the invention those that is applied from a phase liquid on a substrate and form a protective surface or functional and / or decorative, with film formation. How substrates should include, for example, wood, metals, sheets of plastic, pieces of plastic, paper, leather, finger and toe nails and building materials, such as masonry, concrete and plasters. It can be depigmented varnishes, pigmented and containing dyes, which, again, can contain various types of binders, alone or in mixture, such as polyester resins, epoxy resins, resins polyurethane, acrylate and methacrylate resins, resins acrylate-aminoplastics, resins of acrylate isocyanate, nitrocellulose, acetobutyrate of cellulose, alkyd-aminoplast resins, resins alkyds, melamine resins, urea resins, resins silicone, etc., unsaturated or saturated. As a solvent, these varnishes may contain organic solvents and / or softeners, such as esters, ketones, aromatics, aliphatics and alcohols and / or water, as the specialist knows according to the state of technique Very frequently substances are thixotropized adhesive with SiO2. This serves for the best stability over vertical surfaces, as well as for the impediment of runoff They are appropriate binders for these substances adhesives, for example, epoxy resins, resins of polychloroprene, polyurethane resins (mono- and bi-component) and polyacrylate resins. At scope of sealants and flashing are frequently used, by example, acrylic resins, butyl rubber, polysulphurized rubber, epoxy resins and polyurethanes. Also in these systems are employs highly dispersed SiO2 to obtain high stability and thixotropy. Plastisols consist considerably in passable PVC powder or copolymer powder PVC and gelling softeners, such as dioctylphthalate, diisodecylphthalate, dioctyldipate, dioctylsebacate, butylbenzylphthalate and tricresyl phosphate. By SiO 2, prepares a thixotropy, and increases the veil limit and, with it, it prevents draining or impregnation through a textile fabric carrier or other carrier material, such as fabric of fiberglass. They are areas of employment, for example, protection of car basses, sealants, synthetic leather, tarpaulins, pavements and diving items. Nail lacquers are also interesting derivatives of ordinary varnishes and have the same problem of deposit of pigments and therefore must be adjusted rheologically, without the lacquer application process on Nails are damaged. Also, in printing inks regularly use SiO2 to increase viscosity. This employment is a conventional application of lacquers, very similar to as described above, especially as regards pigmentation, solvent and binder; also being used in this context, for example, alcohols, esters, ketones, glycol ethers, water and hydrocarbons, as solvent. The binders are selected according to the purpose of use of the printing ink, for example, modified rosin resins, resin and hydrocarbon resins for printing inks gravure or poly resins, acrylic resins and resins polyamide for inks for packaging. It is understood by masses of molding those masses, which are transformed to give structures, where the reaction resins contained in the masses, as a rule generally at higher temperatures, they are reacted during conformed. They are masses of molding in the sense of the invention, by example, those based on polyester and vinyl resins unsaturated, also in combination with thermoplasts such as polystyrene, polyvinylacetate, polymethylmethacrylate and copolymers styrene-butadiene, which are added to the resins of polyester as a shrinkage reduction percentage. Other masses of molding are, in particular, polyurethanes, which are used, by example, in the reaction-molding process by injection. Other molding doughs can also be prepared based of epoxy resins. These epoxy resins are used preferably in the field of molding and pressing doughs. Other molding masses, which can be transformed, for example, after the wet pressing procedure, injection procedure or Profile drawing procedure, are the resins of phenol-formaldehyde condensation, which are known also under the term of phenolic resins. Molding masses in general they may also contain the usual additives according to to the state of the art or other components. These molding masses they can contain especially fillers and / or materials hardened fillers, such as glass fibers, fibers carbon and polyamide fibers, wollastonites, silicates, inorganic carbonates, aluminum hydroxide, barium sulfate and kaolin. It is very especially preferred in the sense of the invention the use of the agent according to the invention in rolling resins and thin layers (gel coating). In the case of resins of laminate is about systems, which in principle correspond to said molding masses, the hardening as a rule only at room temperature. It is, therefore, cold hardened systems, in contrast with the molding masses previously described. They are rolling resins, for example, those based on resins of polyester, vinyl resins and epoxy resins, unsaturated. These rolling resins are usually hardened by glass fibers and carbon fibers and may contain materials of filler such as Al (OH) 3, CaO 3, Sb 2 O 3, as well as other inorganic and organic pigments, in addition to other auxiliaries necessary for processing, such as Meet the expert. For thin layers (gel coatings) it is the aforementioned rolling resin, where the considerable differences are that normally set higher stability requirements for layer resins fine, especially when it comes to water resistance and in the open. In addition, these thin-layer resins may contain dye pigments, although they usually do not contain any hardening substance. These thin-layer resins are thixotropized in general more strongly than rolling resins.

Thixotropization has special significance in these systems, then, on the one hand, a good penetration of liquid resins in structures in layers of the reinforced fibers and, on the other hand, after a designated Relaxation time should avoid the exit of the resins. In In the case of thin layer structures, a good development, despite the high percentage of SiO2. This is achieved by an accentuated thixotropy, such as that obtained in special measure according to the invention. Depending on the system applied the desired thixotropic effect can be adjusted satisfying the application through the added concentrations of the polymeric urea urethanes according to the invention, is say, as the expert knows, behavior is necessary different rheological for the different procedures of application such as rolling, injection or winding. For obtain the desired thixotropic effect in the systems above cited, are preferably added to the polymer systems liquids 0.1-5%, preferably 0.25-3%, very especially 0.5 - 1.5%, based on the active substance, of the Polymeric urea urethanes according to the invention.

The advantage of rheological control agents according to the invention is that they can be added without great technical cost in liquid polymer systems with moderate agitation and do not need any mechanical disintegration system, such as is necessary, for example, in the case of SiO_ {2} or bentonites. Besides, this time it is about fluids and not powders. Polyurea solutions according to the invention can also be added subsequently to liquid polymer systems. In the case of polyureas according to the invention, they are, in addition, reacted systems, which cannot undergo any additional reaction with partially very reactive binders. An in situ formation of polyureas, as described, for example, in EP-A-0 198 519 by the union of amine and isocyanate, is present in the presence of the binder, for example, in unsaturated polyester resins or varnishes of UV-curable acrylate, as the amines react spontaneously with the binders.

In the following Examples 1-24 the elaboration of polyureas is explained by way of example used according to the invention.

Preparation of NCO prepolymers (according to the invention)

Example one

1.2 moles of diphenylmethane diisocyanate (307.3 g) (Suprasec x 1004 former Huntsman polyurethane; NCO content = 32.8%, determined according to DIN EN ISO 9369) are mixed dropwise with 0.2 moles of hydrogenated 1,2-polybutadiene diol (309.5 g) (OH number = 72.5, OH number = mg KOH / g substance, determined according to DIN / ISO 4629) at room temperature with rinse with nitrogen. The temperature is also maintained constant. After the final addition, stir at T = 40 ° C, until that the theoretical content in NCO of 13.6% is reached.

Example 2

1.2 moles of diphenylmethane diisocyanate (305.5 g) (Desmodur 2460 M ex BAYER AG; NCO content = 33%) are mixed drop by drop with 0.2 moles polybutadiene diol (181 g) (OHZ = 124) a 40 ° C with nitrogen rinse. The temperature is also maintained constant. After the final addition, stir at T = 40 ° C, until The theoretical NCO content of 17.3% is reached. The preparation is It finally leads to room temperature.

Examples 3 to 6 are elaborated analogously to the procedure described in Example 1 and Example 7 according to the procedure described in Example 2.

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Prepolymers

Example Diol Contained in NCO Equivalent weight Molar reason CO: OH [%] [g / val] one 1,2-polybutadiene diol hydrogenated 13.6 308.8 6: 1 (OHZ = 72.5) 2 Polybutadiene diol 17.3 242.8 6: 1 (OHZ = 124) 3 Polyesterdiol (OHZ = 107) 16.2 259.2 6: 1 4 Tripropylene Glycol (OHZ = 584) 22.8 184.2 5: 1 5 Polycaprolactondiol (OHZ = 212) 18.6 225.8 5: 1 6 Polypropylene Glycol (OHZ = 112) 15.7 267.5 5.5: 1 7 PEO-b-PPO-b-PEO (OHZ = 40) 8.2 512.2 5: 1

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Preparation of urea urethanes (according to invention)

Example 8

In 337 g of N-methylpyrrolidone 20.7 g of LiNO 3 and 49.4 g of the mixture are dissolved at 60 ° C amines (equivalent weight = 98.7 g / val; 44.5 g of benzylamine and 4.9 g of 1,6-diaminohexane). Then, they are introduced to 80 ° C for 1 hour 154.4 g of the NCO prepolymers made according to Example 1. After the addition made, stir still for 1 hour and then cool to temperature ambient. The urea urethane solution thus obtained has a solids content of 40% by weight. You get a clear product, long term stable.

Example 9

In 231.5 g of N, N-dimethylacetamide dissolve at 60 ° C 14.8 g of LiCl and 53.2 g of the mixture of amines (equivalent weight = 106.4 g / val; 49.5 g of benzylamine and 3.7 g of 4,4'-diaminodiphenylmethane). Then they are introduced at 60 ° C for 45 minutes 121.4 g of the NCO prepolymers prepared according to Example 2. After the addition made, stir still for 1½ hours and then cool to temperature ambient. The urea urethane solution thus obtained has a solids content of 45% by weight. You get a clear product, long term stable.

one

2

Results of technical use

Serie one

Urea urethanes were studied according to the invention in the following systems, depending on their capacity for the formation of gel type structures.

1) Macrynal SM 510 N: saturated polyester, dissolved at 60% in Xilol.

2) softener / softener: butylbenzylphthalate, 100%

1.0% (based on the active substance) of a urea urethane made according to the invention and an example Comparison of US-A-6 420 466 SE incorporates by simple agitation with the spatula in the system of tests. The evaluation is carried out visually after 24 hours.

TABLE 1

Example Gel consistency in Consistency gel in Macrynal SM 510 N butylbenzylphthalate (BBP) Ex. comp. from the 2 6 US-A-6 420 466 8 one 5 9 2 5 10 one 5 eleven one 3 12 one 5 13 one one 14 one one fifteen one 4 16 one one 17 one one 18 one one 19 one 2 twenty one 4 twenty-one one 3 22 one 5 2. 3 one 2 24 one 2 1 compact structure 2 gel type structure 3 strong structure 4 structure 5 little structure 6 no structure

Serie 2

Urea urea conforming to the invention in polyester unsaturated resins based on their Stability and anti-separation power. The following were used UP resins:

Palatal P 4: diluted (with styrene) according to the technique up to 58% of bodies solid and pre-accelerated with 1% {} \ hskip1.59cm co-dissolution) (DSM)

Palapreg P 18-03: solid body = 65%, 35% styrene (DSM)

1.5% (based on the active substance) of a urea urethane made according to the invention and an example Comparison of US-A-6 420 466 SE Knead with moderate agitation (Dispermat, 500 rpm, 0.75 m / s) in Palatal P 4. After one hour the discharge test is carried out at 50-500 µm. For this purpose the mixture is applied after  Kneading the hardener (Butanox M 50) with a scraper staggered

Assessment: stability (layer thickness) in µm.

0.5% (based on the active substance) of a urea urethane made according to the invention and an example Comparison of US-A-6 420 466 SE introduce with moderate agitation (Dispermat, 500 rpm, 0.75 m / s) in the test system (100 parts of Palapreg P 18-03; 20 parts hollow glass spheres of the type Scotchlite K 37). The samples are transferred to a glass cylinder with closure (> = 3 cm) and stored for five days at 50 ° C

Assessment: height of the fluid column (in cm) as a measure for anti-separation properties:

0 cm: excellent stabilization, homogeneous sample, no flotation of the spheres hollow glass

2 cm: insufficient stabilization, hollow glass spheres float

TABLE 2

Example Gel consistency in Stability in Anti-separation power in UP-Palatal resin P 4 UP-Palatal resin P 4 UP-resin Palapreg P 03-18 Eg comp. from the one 125 µm 2.0 cm US-A-6 420 466 8 one 150 µm 1.2 cm 10 one 200 µm 1.8 cm eleven one 175 µm 0 cm 13 one 250 µm 0 cm 14 one 200 µm 0 cm fifteen one 250 µm 0 cm 16 one 200 µm 0 cm 17 one 200 µm 0.3 cm 19 one 175 µm 1.8 cm

Serie 3

A fixed objective was the elimination of sedimentation of fillers in a resin mass epoxy for the field of electromolding resins.

0.5% (based on the active substance) of a urea urethane made according to the invention and an example Comparison of US-A-6 420 466 SE incorporate for 1 min at 930 rpm (1.5 m / s) in the Dissolver at a epoxy system (25 parts of Ruetapox VE 4518 epoxy resin K.A; 9 parts o-cresylglycidyl ether Ruetapox EPD KR; 44 parts W12 EST quartz flour and 22 parts hydroxide Martinal aluminum ON 310, all components ex Baquelita AG). 100 parts of this filled system are mixed after a useful time of 24 hours with 20 parts of an epoxy resin hardener (Ruetapox VE 4518 K. B ex Baquelita AG) and 0.3 parts of benzyldimethylamine (Ruetapox BDMA ex Baquelita AG) for 2 min at 930 rpm in the Dissolver. This mixture is discharged into a PE glass and it hardens for 2 hours at 95 ° C. The hardened body is cut, if desired, a lower and upper slice of 1 cm thick. A part of this sample body is calcined for 2 hours at 1000 ° C, the filling ratio is determined and thus the sedimentation.

TABLE 3

Mixture resin / hardener Additive Hardening ratio from filling for 2 h at 95 ° C lower Higher Test 0 55.70% 42.90% Comparative example of the US-A-6 420 466 51.20% 45.80% Ex. 14 (according to the invention) 48.20% 48.00%

The values show, that with urea urethane prepared according to the invention a regular distribution is obtained of the filling materials also under intensified conditions of hardening, that is, no sedimentation.

Claims (18)

1. Urea polymeric urea, obtainable by a first reaction of a disocyanate with a polyol, in which disocyanate is used excessively to form a prepolymer NCO double-terminated urethane, in addition to dissociation in excess, and followed by a second reaction of the double mixture NCO double termination urethane prepolymer and disocyanate in excess, on the one hand, with a mixture of a primary monoamine and a primary diamine, on the other hand; in which based on 100 equivalents of the mixture of primary monoamine and primary diamine 0.1 to 45 equivalents of the diamine are used, with the condition of, that after the second reaction the polymer urea urethane is is considerably free of isocyanate and monoamine and the diamine used, and can also be used as a dissociation, polyol, monoamine and diamine mixtures of disocyanates, polyols, monoamines or diamines. 2. Polymeric urea urea according to Claim 1, wherein the disocyanate has the general Formula (I) OCN-R1 -NCO and / or the polyol, the general Formula (II) (II) HO-R2 -OH and / or monoamine, the Formula general (III), R 3 -NH 2 and / or the diamine the general Formula (IV) (IV), H 2 N-R 4 -NH 2 Y where R1 is a linear alkyl radical or branched with 1 to 8 carbon atoms, a radical cycloaliphatic, an arylenic radical or an aralkylene radical, where the aforementioned radicals are substituted, if desired, by C 1 - to C 4 - alkyl groups, R2 is a polyester radical, radical polyether, mixed polyester-polyether radical, polycarbonate radical, polyolefin radical, where a part of the polyethers contained in the aforementioned compounds are replace, if desired, with styrene oxide, R 3 is a linear alkyl radical or branched with 2 to 8 carbon atoms, a radical cycloalkyl, an arylenic radical or an aralkylene radical, where the aforementioned radicals, if desired, contain one or more heteroatoms and / or substituted with C 1 -a alkyl radicals C 4 - and / or alkoxy radicals or R 3 is a radical of the type aryl-CO-NH-, R 4 is a linear alkyl radical or branched with 1 to 12 carbon atoms, a radical cycloaliphatic, a polyether radical, an arylenic radical or a aralkylenic radical, where the aforementioned radicals are replace, if desired, with C 1 -a alkyl radicals C 4 - or R 4 is a radical of the type -NH-CO-R 5 -CO-NH-, where R 5 is a linear alkyl radical with 1 to 8 atoms of carbon, a simple bond or an arylene radical. 3. Polymeric urea urethane according to Claim 1 or 2, wherein the double urethane prepolymer NCO termination is formed by n molecules of disocyanate and n-1 polyol molecules and n amounts to 2 to 6, preferably from 2 to 4. 4. Polymeric urea urethane according to one of Claims 1 to 3, wherein the reaction of the mixture of the NCO double termination urethane prepolymer and disocyanate in excess, on the one hand, with the mixture of primary monoamine and The primary diamine, on the other hand, is made in a solvent aprotic polar 5. Polymeric urea urethane according to one of Claims 1 to 4, wherein the reaction of the mixture of the double NCO double ended urethane prepolymer and the excess disocyanate, on the one hand, with the monoamine mixture primary and primary diamine, on the other hand, is done in presence of a soluble lithium salt. 6. Polymeric urea urethane according to one of Claims 1 to 5, wherein the polyol is a diol. 7. Polymeric urea urethane according to Claim 6, wherein the diol has an average molecular weight of 100 to 4000 g / mol. 8. Polymeric urea urethane according to the Claim 6 or 7, wherein the diol is chosen from compounds of the group consisting of polyester diols, polyether diols, diols of mixed polyester and polyether, polycarbonate diols, polyolefin diols, bonded polyoxypropylene glycols of polyoxyethylene; as well as derivatives of the compounds before mentioned in which also styrene oxide is incorporated by copolymerization; or mixtures of these compounds. 9. Polymeric urea urethane according to one of Claims 1 to 8, wherein the excess disocyanate is calculates against polyol so that more than two are used equivalents of disocyanate per equivalent of polyol. 10. Polymeric urea urethane according to one of Claims 1 to 9, wherein the mixture is first isolated from the First reaction, composed of double urethane prepolymer NCO termination and excess dissociation, and the second reaction is temporarily carried out separately, adding the mixture of the first reaction to a solution of the monoamine mixture primary and primary diamine in an aprotic polar solvent, if desired, in the presence of a lithium salt dissolved in the solvent aprotic polar 11. Polymeric urea urethane according to one of Claims 1 to 10, wherein 1 to 35 is used, preferably 3 to 25 equivalents of the diamine, based on 100 equivalents of the mixture of primary monoamine and diamine primary. 12. Procedure for the preparation of polymeric urea urethanes according to one or more of the Claims 1 to 11, where a first reaction is made reacting a disocyanate with a polyol, in which the disocyanate is used excessively to form a double urethane prepolymer NCO termination, in addition to excess disocyanate, and followed by a second reaction of the mixture of the double urethane prepolymer of double NCO termination and excessive dissociation, on the one hand, with a mixture of a primary monoamine and a primary diamine, on the other hand; in which based on 100 equivalents of the mixture of Primary monoamine and primary diamine are used from 0.1 to 45 equivalents of the diamine, with the proviso that after the second reaction urea polymeric urethane is found considerably free of isocyanate and monoamine and diamine used, and can also be used as disocyanate, polyol, monoamine and diamine mixtures of disocyanates, polyols, monoamines or diamines, respectively. 13. Procedure for the preparation of polymeric urea urethanes according to Claim 11, wherein the disocyanate has the general Formula (I) OCN-R1 -NCO and / or the polyol, the general Formula (II) (II) HO-R2 -OH and / or monoamine, the Formula general (III), R 3 -NH 2 and / or the diamine the general Formula (IV) (IV), H 2 N-R 4 -NH 2 Y where R1 is a linear alkyl radical or branched with 1 to 8 carbon atoms, a radical cycloaliphatic, an arylenic radical or an aralkylene radical, where the aforementioned radicals are substituted, if desired, by C 1 - to C 4 - alkyl groups, R2 is a polyester radical, radical polyether, mixed polyester-polyether radical, polycarbonate radical, polyolefin radical, where a part of the polyethers contained in the aforementioned compounds are replace, if desired, with styrene oxide, R 3 is a linear or branched alkyl radical with from 2 to 8 carbon atoms, a cycloalkyl radical, an arylenic radical or an aralkylene radical, where the aforementioned radicals, if desired, contain one or more heteroatoms and / or they are substituted with C 1 - to C 4 alkyl radicals and / or alkoxy radicals or R 3 is a radical of the aryl-CO- type
NH-, R 4 is a linear alkyl radical or branched with 1 to 12 carbon atoms, a radical cycloaliphatic, a polyether radical, an arylenic radical or a aralkylenic radical, where the aforementioned radicals are replace, if desired, with C 1 -a alkyl radicals C 4 - or R 4 is a radical of the type -NH-CO-R 5 -CO-NH-, where R 5 is a linear alkyl radical with 1 to 8 atoms of carbon, a simple bond or an arylene radical. 14. Procedure for the preparation of polymeric urea urethanes according to one of the Claims 12 or 13, where the first reaction mixture is first isolated, composed of NCO double termination urethane prepolymer and excess disocyanate, and the second reaction is carried out temporarily separately, adding the mixture of the first reaction to a solution of the primary monoamine mixture and primary diamine in an aprotic polar solvent, if desired, in presence of a lithium salt dissolved in the polar solvent aprotic 15. Procedure for the preparation of polymeric urea urethanes according to one of the Claims 12 to 14, where 1 to 35 is used, preferably 3 to 25 equivalents of the diamine, based on 100 equivalents of the mixture of primary monoamine and primary diamine. 16. Use of the corresponding urea polymer urethane to one of Claims 1 to 11 as a control agent rheological in liquid polymer systems. 17. Use of polymeric urea urethane according to claim 16, wherein the polymer systems they contain solvents, which, if desired, are reactive against polymer dissolved in the polymer system. 18. Use of the corresponding urea polymer urethane to one of Claims 16 or 17, wherein the polymer system It is a coating agent, floor covering material, adhesive, laminate resin, gel coating, plastisol PVC, a molding mass, sealant, flashing, plaster or ink printing and, if desired, contains fillers and / or pigments and / or binder.